CN103459579B - Liquid washing agent - Google Patents

Liquid washing agent Download PDF

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Publication number
CN103459579B
CN103459579B CN201280016756.4A CN201280016756A CN103459579B CN 103459579 B CN103459579 B CN 103459579B CN 201280016756 A CN201280016756 A CN 201280016756A CN 103459579 B CN103459579 B CN 103459579B
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disperse blue
liquid washing
blue
washing agent
quality
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CN103459579A (en
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神藤宏明
黑川贵行
小仓弘嗣
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Lion Corp
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Lion Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

Abstract

A kind of liquid washing agent, contains: the urea or derivatives thereof (C) of the tensio-active agent (A) of more than 40 quality %, the pigment (B) of below quality criteria 150ppm, 0.5 ~ 12 quality %.

Description

Liquid washing agent
Technical field
The present invention relates to a kind of liquid washing agent containing urea.
CLAIM OF PRIORITY based on No. 2011-081768, the patent application Patent that the application proposed in Japan by April 1st, 2011, quotes its content at this.
Background technology
Recently, as the washing composition that home washings uses, liquid washing agent is owing to having the speciality (such as: without dissolving residual, pleasure enjoy fragrance etc.) different from washing powder, and price is reasonable grounds also, and its demand is just at expanding day.
About liquid washing agent, there is the unsatisfied place of human consumer such as " the hand-held container that liquid washing agent is housed is very heavy ", " bringing back inconvenience of returning home from shop ", " having used up soon ".
On the other hand, at detergent applications, surging due to what realize carrying capacity of environment, seeking to reduce each washing usage quantity of washing composition, resin is discarded to be measured to reduce in the miniaturization of the container dimensional of accommodation washing composition.
For so dissatisfied, requirement, as the composition of liquid washing agent, develop a kind of tensio-active agent containing high density, each washing can with the composition of the what is called " concentrated type " of former usage quantity half.
Tensio-active agent containing proportional high liquid washing agent along with the increase of time, especially on fluid surface, the easy gelation of aforesaid liquid washing composition self, produces the problem that usability is deteriorated thus.Once liquid washing agent gelation, liquid washing agent is difficult to carry out measuring (that is, measuring) with bottle cap, is also deteriorated from bottle cap to the property poured out of washing machine input port simultaneously.Thus, about concentrated type liquid washing agent, except requiring high cleaning force, also require that increase in time gelation etc. does not occur and keeps mobility, well fluid.
To this, disclose and a kind ofly use specific polyoxyethylene fatty acid methyl esters as the concentrated type liquid washing agent (referenced patent document 1,2) of tensio-active agent.
In addition, when measuring liquid washing agent with bottle cap, when outward appearance is water white liquid, owing to being difficult to contrast with the scale of bottle cap, therefore the amount of liquid that measures of bottle cap easily than during specified amount too much or time and very few.Especially the situation of concentrated type liquid washing agent, from the viewpoint of can than ever usage quantity reduce, therefore correctly measure very important with bottle cap.
For such problem, do to make an effort: coordinate pigment to make liquid washing agent painted, further bottle cap is made transparent, the amount making liquid washing agent bottle cap measure thus is easily differentiated, and is easy to metering.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2008-7706 publication
Patent documentation 2: Japanese Patent Laid-Open 2008-7707 publication
Summary of the invention
But about the concentrated type liquid washing agent containing pigment, there are the following problems: the washing object (washing clothes) being coated with aforesaid liquid washing composition through a placement round the clock or rinsing insufficient time, washing clothes is easily by pigment dyeing.
The present invention completes in view of the foregoing, and its problem is: in the concentrated type liquid washing agent containing pigment, provides a kind of while having high cleaning force, also can suppress the liquid washing agent to washing clothes pigment dyeing.
The present inventor, through constantly making great efforts the result of research, provides following means to solve above-mentioned problem.That is, the first form of the present invention is the liquid washing agent containing the tensio-active agent (A) of more than 40 quality %, the pigment (B) of below quality criteria 150ppm, the urea or derivatives thereof (C) of 0.5 ~ 12 quality %.
Second form of the present invention is in the liquid washing agent of above-mentioned first form, the liquid washing agent of above-mentioned tensio-active agent (A) containing at least one tensio-active agent be selected from nonionogenic tenside that following general formula (a1) ~ (a3) represent.
[changing 1]
R 1CO-(OR 2)s-OR 3···(a1)
R 4-O-(R 5O)t-H···(a2)
R 6-O-[(EO)p/(PO)q]-(EO)r-H···(a3)
[in formula (a1), R 1for the straight-chain of carbonatoms 5 ~ 21 or the alkyl of branched or thiazolinyl, R 2for the alkylidene group of carbonatoms 2 ~ 4, R 3for the alkyl of carbonatoms 1 ~ 4, s represents OR 2average repeat unit number, be the integer of 5 ~ 30; In formula (a2), R 4for the alkyl of carbonatoms 10 ~ 22, R 5for the alkylidene group of carbonatoms 2 ~ 4, t represents R 5the average repeat unit number of O is the integer of 5 ~ 20; In formula (a3), R 6for alkyl or the thiazolinyl of carbonatoms 10 ~ 16, p represents the average repeat unit number of EO, q represents the average repeat unit number of PO, r represents the average repeat unit number of EO, p, q, r are the integer meeting p > 1, r>=0,0 < q≤3 and p+r=10 ~ 30, EO represents oxyethylene group, and PO represents oxypropylene group, EO and PO in (EO) p/ (PO) q also can mix arrangement.]
In addition, the 3rd form of the present invention is in the liquid washing agent of the above-mentioned first or second form, contains the liquid washing agent of the organic solvent (D) that following general formula (d1) represents further.
[changing 2]
R 7-[(EO)n/(PO)m]-H···(d1)
[in formula, R 7for the alkyl of hydrogen atom, hydroxyl or carbonatoms 1 ~ 4; M represents the average repeat unit number of PO, and n represents the average repeat unit number of EO, and m is the integer of 0 ~ 2, and n is the integer of 0 ~ 3, and 1≤m+n≤5; EO represents oxyethylene group, and PO represents oxypropylene group, EO and PO also can mix arrangement.]
According to the present invention, in the concentrated type liquid washing agent containing pigment, can be provided in while there is high cleaning force, the liquid washing agent to washing clothes pigment dyeing can be suppressed.
Embodiment
Liquid washing agent of the present invention, the urea or derivatives thereof (C) of the tensio-active agent (A) containing more than 40 quality %, the pigment (B) of below quality criteria 150ppm, 0.5 ~ 12 quality %.
Below, these three kinds of compositions are called (A) composition, (B) composition, (C) composition sometimes.
[tensio-active agent (A)]
As tensio-active agent (A), nonionogenic tenside, anion surfactant, cats product, amphoterics etc. can be mixed and be generally used for the tensio-active agent that clothing washes agent by liquid.
(nonionogenic tenside)
As nonionogenic tenside, tensio-active agent and polyoxyalkylene alkyl that following general formula (a1) ~ (a3) represent can be enumerated.
[changing 3]
R 1CO-(OR 2)s-OR 3···(a1)
[in formula (a1), R 1for the straight-chain of carbonatoms 5 ~ 21 or the alkyl of branched or thiazolinyl, R 2for the alkylidene group of carbonatoms 2 ~ 4, R 3for the alkyl of carbonatoms 1 ~ 4, s represents OR 2average repeat unit number, be the integer of 5 ~ 30.]
In above-mentioned formula (a1), R 1for the straight-chain of carbonatoms 5 ~ 21 or the alkyl of branched, or the straight-chain of carbonatoms 5 ~ 21 or the thiazolinyl of branched.
From the viewpoint of improving cleaning force and storage stability, R 1the carbonatoms of middle alkyl and thiazolinyl respectively preferably 9 ~ 13, more respectively preferably 11 ~ 13.
As abovementioned alkyl, specifically can illustrate C 11h 23, C 13h 27deng.
As above-mentioned thiazolinyl, specifically can illustrate C 11h 21, C 13h 25deng.
R 2for the alkylidene group of carbonatoms 2 ~ 4, the alkylidene group of preferred carbonatoms 2 ~ 3, more preferably vinyl.In addition, (OR 2) s can be a kind of independent oxyalkylene group repeating unit structure, also can mix the oxyalkylene group of more than two kinds.When mixing the oxyalkylene group of more than two kinds, oxyalkylene group can block-wise addition, also can random shape addition.
R 3for the alkyl of carbonatoms 1 ~ 4, preferable methyl.
In above-mentioned formula (a1), s represents OR 2average repeat unit number, be the integer of 5 ~ 30.From the viewpoint of the liquid stability (particularly low temperature ageing stability etc.) improving cleaning force and liquid washing agent, s preferably 12 ~ 18.
In the composition that above-mentioned formula (a1) represents, for representing OR 2the stenosis rate (narrowrate) of the compound distribution proportion that number of repeat unit is different is preferably at more than 20 quality %.The higher limit of stenosis rate is preferably in fact at below 80 quality %.That is, this stenosis rate preferably 20 ~ 80 quality %, more preferably 20 ~ 60 quality %, further preferred 30 ~ 45 quality %.Above-mentioned stenosis rate is higher, more can obtain good cleaning force, but too high, and likely low temperature ageing stability declines.
" stenosis rate " in this specification sheets refers to, the numerical value represented by following mathematical formula (S).
[several 1]
In above-mentioned formula (S), S maxrepresent in the composition entirety that above-mentioned formula (a1) represents the alkylene oxide addition mole number that there is maximum alkylene oxides and add adult.
I represents the addition mole number of alkylene oxide.Yi represents that the alkylene oxide addition mole number existed in the composition entirety represented in above-mentioned formula (a1) is the ratio (quality %) that the alkylene oxide of i adds adult.
The manufacture method etc. of the composition that above-mentioned stenosis rate can be represented by above-mentioned (a1) controls.
The manufacture method of the composition that above-mentioned formula (a1) represents is not particularly limited, as an example, by using the O composite metallic oxide catalyst of surface modification, the method (with reference to Japanese Patent Laid-Open 2000-144179 publication) according to addition polymerization alkylene oxide on fatty acid alkyl ester can easily manufacture.
As the Suitable examples of the multiple containing metal oxide catalyzer of this surface modification, specifically have: with metal hydroxides etc. carry out surface modification, with the addition of metal ion (Al 3+, Ga 3+, In 3+, Tl 3+, Co 3+, Sc 3+, La 3+, Mn 2+deng) the O composite metallic oxide catalyst such as magnesium oxide; Or the calcined material catalyzer etc. of the hydrotalcite of surface modification is carried out with the compound being selected from least one in metal hydroxides and metal alkoxide etc.In addition, in the surface modification of above-mentioned O composite metallic oxide catalyst, complex metal oxides with the blending ratio of the compound being selected from least one in metal hydroxides and metal alkoxide is: relative to complex metal oxides 100 mass parts, the ratio being selected from the compound of at least one in metal hydroxides and metal alkoxide is preferably set to 0.5 ~ 10 mass parts, is more preferably set in 1 ~ 5 mass parts.
[changing 4]
R 4-O-(R 5O)t-H···(a2)
[in formula (a2), R 4for the alkyl of carbonatoms 10 ~ 22, R 5for the alkylidene group of carbonatoms 2 ~ 4, t represents R 5the average repeat unit number of O is the integer of 5 ~ 20.]
In above-mentioned formula (a2), R 4carbonatoms be 10 ~ 22, preferably 10 ~ 20, more preferably 10 ~ 18.R 4in alkyl can be straight-chain also can be branched, can also unsaturated link(age) be had.As R 4in alkyl, specifically there are C 10h 21, C 12h 25, C 14h 29, C 16h 33, C 18h 37, C 20h 41deng.
The composition that the composition that above-mentioned formula (a2) represents can be made up of single chain length also can be the mixture with multiple chain long component.As the raw material during composition represented for the synthesis of above-mentioned formula (a2), the alcohol being derived from the natural fats and oils such as Oleum Cocois, plam oil, butter, the synthol etc. being derived from oil can be used.
In above-mentioned formula (a2), R 5for the alkylidene group of carbonatoms 2 ~ 4, the alkylidene group of preferred carbonatoms 2 ~ 3, more preferably vinyl.In addition, (R 5o) t can be a kind of independent oxyalkylene group repeating unit structure, also can more than two kinds oxyalkylene group mixing existence.The oxyalkylene group mixing of more than two kinds is when existing, and oxyalkylene group can with block-wise addition, also can with random shape addition.
In above-mentioned formula (a2), t represents R 5the average repeat unit number of O is the integer of 5 ~ 20, the preferably integer of 8 ~ 18, the more preferably integer of 10 ~ 16.If t is more than 20, because HLB becomes too high, unfavorable to sebum cleaning, thus cleansing power easily declines.If t is more than 5, then easily prevent the deterioration of foul smell.Particularly, t, when the scope of 10 ~ 16, demonstrates high cleaning force to sebum spot.
R 5o addition mole number distribution along with preparation above-mentioned formula (a2) represent composition time reaction method and change, be not particularly limited.Such as, use the alkaline catalystss such as general sodium hydroxide or potassium hydroxide, when alkylene oxide being added on hydrophobic group raw material, R 5the addition mole number distribution of O has more eurytopic tendency.In addition, with the addition of Al when what record in use Japanese Patent Laid-fair 6-15038 publication 3+, Ga 3+, In 3+, Tl 3+, Co 3+, Sc 3+, La 3+, Mn 2+specific alkane oxidation catalyst such as magnesium oxide etc. Deng metal ion, when alkylene oxide being added on hydrophobic group raw material, R 5the addition mole number of O distributes the tendency had compared with narrow ditribution.
As the object lesson of the composition that above-mentioned formula (a2) represents, for example there are: the composition that the alcohol addition of the Safol23 (C12/C13) that the commodity Neodol (mixture of the alcohol of carbonatoms 12 and the alcohol of carbonatoms 13: be sometimes referred to as C12/C13 below), the Sa Suoer company that produce Shell Co. Ltd produce etc. is equivalent to 12 or 15 moles of ethylene oxide and obtains; The trade(brand)name CO-1214 produce P & G company and the natural alcohol addition such as CO-1270 are equivalent to the oxyethane of 9,12 or 15 moles and the composition that obtains; Secondary alcohol addition to carbonatoms 12 ~ 14 is equivalent to the oxyethane of 9,12 or 15 moles and the composition (SOFTANOL90,120 or 150 that Nippon Shokubai Co., Ltd produces) etc. that obtains.
[changing 5]
R 6-O-[(EO)p/(PO)q]-(EO)r-H···(a3)
[in formula (a3), R 6for alkyl or the thiazolinyl of carbonatoms 10 ~ 16, p represents the average repeat unit number of EO, q represents the average repeat unit number of PO, r represents the average repeat unit number of EO, p, q, r are the integer meeting p > 1, r>=0,0 < q≤3 and p+r=10 ~ 30, EO represents oxyethylene group, PO representative ring oxypropylene group, EO and PO in (EO) p/ (PO) q also can mix arrangement.]
In above-mentioned formula (a3), R 6in alkyl, thiazolinyl carbonatoms be 10 ~ 16, preferably 10 ~ 14.R 6in alkyl and thiazolinyl can be straight-chain, also can be branched.
As the alkyl of above-mentioned straight-chain or branched, concrete example has: C 10h 21, C 12h 25, C 14h 29deng.
As the thiazolinyl of above-mentioned straight-chain or branched, concrete example has: C 10h 19, C 12h 23, C 14h 27deng.In above-mentioned formula (a3), r is r >=0, preferred r >=1.P+r=10 ~ 30, preferred p+r=14 ~ 20.
In above-mentioned formula (a3), the ratio of EO and PO, the ratio represented with q/ (p+r) preferably 0.1 ~ 0.5, more preferably 0.1 ~ 0.3.When the ratio represented with q/ (p+r) is more than lower value, can not excess foam formation, the foaming of appropriateness can be obtained.When the ratio represented with q/ (p+r) is below higher limit, be easy to the viscosity obtaining appropriateness, be easy to suppress gelation.In addition, when q is below 3, biodegradability improves.
(EO) EO and PO in p/ (PO) q, can only have one of them existence arbitrarily, also can mix arrangement.(EO) EO and PO in p/ (PO) q can random shape addition, also can block-wise addition.
The composition that above-mentioned formula (a3) represents can synthesize according to known method.As an example, after the alcohol derived by natural fats and oils carries out addition reaction with oxyethane and propylene oxide successively or after mixing addition of ethylene oxide and propylene oxide (random addition), addition of ethylene oxide again, can synthesize the composition that above-mentioned formula (a3) represents thus.
As polyoxyalkylene alkyl, there are: on the fatty alcohol of carbonatoms 6 ~ 22, preferably carbonatoms 8 ~ 18, generate polyoxyalkylene alkyl with the oxyalkylene of average 3 ~ 30 moles, preferably 5 ~ 20 moles of addition carbonatomss 2 ~ 4, or polyoxyalkylene alkenyl ether (alcohol alkoxide).Wherein, preferred Voranol EP 2001, polyoxyethylene alkene ether, polyoxyethylene polyoxy-propylene and polyoxyethylene polyoxypropylene alkene ether.
As fatty alcohol as used herein, for example there are: primary alconol or secondary alcohol.The alkyl of fatty alcohol can have side chain.As the preferred primary alconol of fatty alcohol.
(anion surfactant)
As anion surfactant, for example there are: alkylbenzene sulfonate, alkyl-sulphate, secondary alkyl sulfonate, polyoxyethylene alkyl ether sulfate salt, α olefin sulfonate, alpha-sulfo fatty acid ester salt, Voranol EP 2001 carboxylate salt etc.
As anion surfactant, specifically there can be exemplified: the linear alkylbenzene sulfonate (LAS) with carbonatoms 8 ~ 16 (preferred carbonatoms 10 ~ 14) alkyl; There is the alkyl-sulphate (AS) of carbonatoms 10 ~ 20 alkyl; There is carbonatoms 10 ~ 20 (preferred carbonatoms 10 ~ 14) alkyl and the polyoxyethylene alkyl ether sulfate salt (AES) of the average addition mole number 1 ~ 10 (preferably average addition mole number 1 ~ 4) of oxyethane; There is the α olefin sulfonate (AOS) of carbonatoms 10 ~ 20 alkyl; There is the secondary alkyl sulfonate (SAS) of carbonatoms 10 ~ 20 (preferred carbonatoms 10 ~ 14) alkyl; There is the α-sulfofattyacidmethylestersalt (α-SF) of carbonatoms 10 ~ 20 alkyl; There is carbonatoms 10 ~ 20 alkyl and the Voranol EP 2001 carboxylate salt etc. of the average addition mole number 1 ~ 10 of oxyethane.
As the salt of these compounds, for example there are: an alkali metal salt such as sodium salt, sylvite; The alkanol amine salt such as monoethanolamine salt, diethanolamine salt etc., preferred as alkali salt.
As polyoxyethylene alkyl ether sulfate salt; the polyoxyethylene alkyl ether sulfate salt be preferably as follows: when the ethyleneoxide addition molar basis that will there is maximum ethyleneoxide addition bodies in quality criteria in all ethyleneoxide addition bodies forming polyoxyethylene alkyl ether sulfate salt is for " nlmax ", ethyleneoxide addition mole number is (nlmax-1), the summation of the ethyleneoxide addition body of nlmax and (nlmax+1) accounts for the polyoxyalkylene alkyl vitriol of ratio at more than 55 quality % of all ethyleneoxide addition bodies; More preferably at the polyoxyethylene alkyl ether sulfate salt of 55 ~ 80 quality % scopes.If in above-mentioned scope, the mobility of polyoxyethylene alkyl ether sulfate salt improves, and manufacturing improves.
Wherein, as anion surfactant, from the angle that secondary pollution preventive is good, preferred alkyl benzene sulfonate, polyoxyethylene alkyl ether sulfate salt and secondary alkyl sulfonate; More preferably alkylbenzene sulfonate and polyoxyethylene alkyl ether sulfate salt; Particularly preferably alkylbenzene sulfonate.
As cats product, for example there are: alkylamine salt, alkyl quaternary ammonium salts etc.
As amphoterics, for example there are: carboxylic acid type amphoterics (amino acid pattern and betaine type), sulfuric acid ester type amphoterics, sulfonic acid type amphoterics, phosphate type amphoterics etc.
In addition, as other tensio-active agents, also can for example there are: the tensio-active agent, fluorocarbons system tensio-active agent etc. of the derivative of natural surface active agent, protolysate, polymeric surface active agent, titaniferous/silicon.
(A) composition can a kind ofly separately use, also can be two or more and use.
Wherein, as (A) composition, preferably use nonionogenic tenside and anion surfactant.
Particularly, (A) in composition, nonionogenic tenside is preferably contained at more than 50 quality % relative to (A) composition, more preferably nonionogenic tenside is at more than 80 quality %, further preferred nonionic surfactants is at more than 90 quality %, and nonionogenic tenside also can be 100 quality %.By using nonionogenic tenside, even if the tensio-active agent containing high density also gelation etc. can not occur, easily obtain the concentrated type liquid washing agent demonstrating good storage stability.And, owing to being concentrated type liquid washing agent, when using liquid washing agent to washing clothes coating, excellent coating cleaning force can be obtained.
As nonionogenic tenside, from the angle that cleaning force is high, preferably containing at least one nonionogenic tenside be selected from nonionogenic tenside that above-mentioned general formula (a1) ~ (a3) represent.
In addition, as (A) composition, from preventing spot to be again attached to the high angle of secondary pollution preventive on washing clothes washings, preferred nonionic surfactants and anion surfactant are together and use.
In liquid washing agent, the amount of (A) composition is more than 40 quality % relative to liquid washing agent total mass, preferably 40 ~ 70 quality %, more preferably 45 ~ 65 quality %.
(A) if the amount of composition is more than 40 quality % relative to liquid washing agent total mass, effect of the present invention can significantly play.In addition, also good cleaning force can be obtained.And due to the tensio-active agent containing high density, the validity (commodity value) as concentrated type liquid washing agent improves.
(A) amount of composition is relative to liquid washing agent total mass preferably below 70 quality %, and more preferably during below 65 quality %, increase along with the time and not easily occur in the liquid washing agent gelation etc. that fluid surface produces, fluid surface epithelium is not easily formed.
Together and the used time, the amount of anion surfactant is preferably 1 ~ 10 quality % relative to liquid washing agent total mass, more preferably 1 ~ 5 quality % for nonionogenic tenside and anion surfactant, further preferred 2 ~ 5 quality %.
If the amount of anion surfactant is below 10 quality % relative to liquid washing agent total mass, then at the fluid surface of liquid washing agent, aforesaid liquid washing composition self is difficult to gelation, and epithelium is difficult to be formed.In addition, be coated with cleaning force to improve preferably.If the amount of anion surfactant is more than 1 quality % relative to liquid washing agent total mass, then secondary pollution preventive improves further.
[pigment (B)]
Pigment (B) is not particularly limited, and for example there are: matching stain, basic dyestuff, cationic dyestuff, medium (oil soluble) dyestuff, vat dyes, naphthol dye (azoic dyestuff), reactive dye (chemically-reactive dyes), dispersed dye, oxidation dye etc.The structure of each dyestuff is documented in " legal pigment handbook " (Japanese cosmetic industry contact can be compiled).
Wherein, as (B) composition, the angle significantly played is easy to from effect of the present invention, the pigment of maximum absorption wavelength is preferably had at 400 ~ 700nm, more preferably there is the pigment of maximum absorption wavelength at 500 ~ 700nm, have the pigment of the blueness ~ green of maximum absorption wavelength particularly preferably in 590 ~ 650nm.
As pigment (B), specifically, blue series dyestuff shown below, green based dye can be enumerated.
Blue series dyestuff: C.I. acid blue 5, C.I. acid blue 9, C.I. Acid Blue 74, C.I. solvent blue 19 1, C.I. solvent blue 19 2, C.I. solvent blue 36, C.I. solvent blue 63, C.I. EX-SF DISPERSE BLUE EX-SF 300 1, C.I. EX-SF DISPERSE BLUE EX-SF 300 3, C.I. EX-SF DISPERSE BLUE EX-SF 300 5, C.I. EX-SF DISPERSE BLUE EX-SF 300 6, C.I. EX-SF DISPERSE BLUE EX-SF 300 7, C.I. EX-SF DISPERSE BLUE EX-SF 300 26, C.I. EX-SF DISPERSE BLUE EX-SF 300 27, C.I. EX-SF DISPERSE BLUE EX-SF 300 54, C.I. EX-SF DISPERSE BLUE EX-SF 300 55, C.I. Disperse Blue-56, C.I. Disperse Blue-60, C.I. EX-SF DISPERSE BLUE EX-SF 300 61, C.I. EX-SF DISPERSE BLUE EX-SF 300 62, C.I. EX-SF DISPERSE BLUE EX-SF 300 64, C.I. EX-SF DISPERSE BLUE EX-SF 300 72, C.I. EX-SF DISPERSE BLUE EX-SF 300 73, C.I. EX-SF DISPERSE BLUE EX-SF 300 81, C.I. EX-SF DISPERSE BLUE EX-SF 300 87, C.I. EX-SF DISPERSE BLUE EX-SF 300 90, C.I. EX-SF DISPERSE BLUE EX-SF 300 91, C.I. EX-SF DISPERSE BLUE EX-SF 300 97, C.I. EX-SF DISPERSE BLUE EX-SF 300 98, C.I. EX-SF DISPERSE BLUE EX-SF 300 99, C.I. EX-SF DISPERSE BLUE EX-SF 300 103, C.I. EX-SF DISPERSE BLUE EX-SF 300 104, C.I. EX-SF DISPERSE BLUE EX-SF 300 105, C.I. Blue 7, C.I. vat blue 1, C.I. reductive blue 6, C.I. pigment indigo plant 15 etc.
In addition, for solvent system (oil soluble) pigment wherein, also can be carry out chemically modified to increase water miscible pigment at the water-soluble polymer such as end polyoxyethylene glycol or polypropylene glycol of chromophore architectures.Concrete example has: the commodity of the trade(brand)names such as LiquitintBlueHP, LiquitintBlueBL that Mei Liken Co., Ltd. produces.
Green based dye: C.I. acid green 1, C.I. acid green 3, C.I. acid green 5, C.I. ACID GREEN 25, C.I. food indigo plant 2, C.I. Food Green 3, C.I. solvent green 3, C.I. Food Green 3, C.I. solvent are green 7, C.I. solvent is green.
(B) composition can a kind ofly separately use, also can be two or more and use.
From for the dyeability of washing clothes and the angle of mixed liquid color degree, in liquid washing agent, the amount of (B) composition is more than 1ppm (quality criteria), 150ppm (quality criteria) (below 0.015 quality %) below relative to liquid washing agent total mass, preferably 1 ~ 100ppm (quality criteria) (0.0001 ~ 0.01 quality %), more preferably 3 ~ 50ppm (quality criteria) (0.0003 ~ 0.005 quality %).
(B) if the amount of composition does not arrive lower value, the liquid of liquid washing agent likely can not be fully painted.On the other hand, if the amount of (B) composition exceedes higher limit, then likely can not suppress the pigment dyeing to washing clothes completely.
[urea or derivatives thereof (C)]
As urea or derivatives thereof (C), for example there are: urea [CO (NH 2) 2], urea double salt and urea derivative in addition.
As urea double salt, HNO can be used 3cO (NH 2) 2, H 3pO 4cO (NH 2) 2, H 2c 2o 42CO (NH 2) 2, Ca (NO 3) 24CO (NH 2) 2, CaSO 44CO (NH 2) 2, Mg (NO 3) 2cO (NH 2) 22H 2o, CaSO 4(5 ~ 6) 4CO (NH 2) 22H 2o etc.
" derivative of urea " in the present invention comprises the compound with structure shown in following general formula (c1).In urea derivative, the compound that general formula (c1-1) represents can be enumerated.
[changing 6]
In above-mentioned formula (c1-1), R afor the hydroxyalkyl of methyl, ethyl or carbonatoms 1 ~ 2.R b, R cand R dbe hydrogen atom, methyl or ethyl independently of one another.
As the compound that above-mentioned formula (c1-1) represents, for example there are: 1,3-dimethyl urea, N-(2-hydroxyethyl) urea etc.
(C) composition can a kind ofly separately use, also can be two or more and use.
In liquid washing agent, the amount of (C) composition is relative to liquid washing agent total mass preferably 0.5 ~ 12 quality %, more preferably 1 ~ 10 quality %, further preferred 1 ~ 8 quality %.
(C) if the amount of composition does not arrive lower value, the pigment dyeing to washing clothes can not likely fully be suppressed.On the other hand, when the amount of (C) composition exceedes higher limit, after preserving, easily produce resolvent ammonia, as detergent product sometimes smell can become problem.In addition, because easily reduce the affinity of spot, so coating cleaning force likely reduces.
In liquid washing agent of the present invention, the blending ratio of (A) composition and (C) composition, the mass ratio represented in (A)/(C) preferably less than 30, more preferably 6 ~ 15, further preferably 9 ~ 11.
If (A)/mass ratio that (C) represents is below higher limit, then easily suppress the pigment dyeing to washing clothes.On the other hand, when the mass ratio that (A)/(C) represents does not arrive lower value, coating cleaning force likely reduces.
In the present invention, " mass ratio that (A)/(C) represents " represents the amount relative to (C) composition in liquid washing agent, the ratio (mass ratio) of the amount of (A) composition.
[solvent: water]
From easy modulating liquid body washing composition, use time water in the viewpoint such as solvability, liquid washing agent of the present invention preferably containing water as solvent.
In liquid washing agent, the amount of water is preferably 15 ~ 45 quality % relative to liquid washing agent total mass, more preferably 25 ~ 40 quality %.
If the amount of water is more than lower value, then liquid washing agent through time liquid stability become better; If below higher limit, then the appropriate step-down of liquid viscosity, from the viewpoint of usability, better.
[organic solvent (D)]
In liquid washing agent of the present invention, preferably further containing the organic solvent (D) (hereinafter also referred to " (D) composition ") that useful following general formula (d1) represents.By containing (D) composition, coating cleaning force (particularly for the cleaning force of greasy dirt or marker pen spot) improves, and (assuming that winter), the suppression to the pigment dyeing of washing clothes was more prone to especially at low temperatures.In addition, (D) composition as the viscosity modifier of aforesaid liquid washing composition and gelation inhibitors also effective.
[changing 7]
R 7-[(EO)n/(PO)m]-H···(d1)
[in formula, R 7for the alkyl of hydrogen atom, hydroxyl or carbonatoms 1 ~ 4; M represents the average repeat unit number of PO; N represents the average repeat unit number of EO; M is the integer of 0 ~ 2, and n is the integer of 0 ~ 3, and 1≤m+n≤5; EO represents oxyethylene group, and PO represents oxypropylene group, EO and PO also can mix arrangement.]
In above-mentioned formula (d1), R 7for hydrogen atom, hydroxyl or carbonatoms are the alkyl of 1 ~ 4.R 7in alkyl can be straight-chain also can be branched.
As above-mentioned straight-chain and branched-chain alkyl, concrete example has: CH 3, C 2h 5, C 3h 7, C 4h 9deng.(EO) EO and PO in n/ (PO) m can only have one of them existence arbitrarily, also can mix arrangement.(EO) EO and PO in n/ (PO) m can random shape addition, also can block-wise addition.
As (D) composition, for example there are: the alkanols (D1) such as ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol; The aklylene glycol class (D2) such as multipolymer, Diethylene Glycol, triethylene glycol, dipropylene glycol of ethylene glycol, propylene glycol, ethylene glycol and propylene glycol; The carbonatomss such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, TC, diethylene glycol diethyl ether, DPGME, dihydroxypropane single-ethyl ether, diethylene glycol monobutyl ether be 2 ~ 3 aklylene glycol be (gathering) aklylene glycol (the single or two) alkyl oxide (D3) etc. that (gathering) aklylene glycol of unit and the alkanol of carbonatoms 1 ~ 4 are formed.
(D) composition can a kind ofly separately use, also can be two or more and use.
Wherein, as (D) composition, preferably use at least one organic solvent be selected from above-mentioned (D1) ~ (D3), more preferably combinationally use be selected from above-mentioned in two or more organic solvents.By combinationally using two or more organic solvents, easily obtain the viscosity adjustment of liquid washing agent and the inhibition of gelation.
In liquid washing agent, the amount of (D) composition is relative to liquid washing agent total mass preferably 5 ~ 20 quality %, more preferably 5 ~ 18 quality %, further preferred 5 ~ 15 quality %.
(D) amount of composition does not arrive lower value, is difficult to obtain suitable viscosity, and during coating washing clothes, liquid washing agent easily solidifies.On the other hand, if the amount of (D) composition exceedes higher limit, then likely produce the foul smell being derived from (D) composition, and consider also not preferred from the angle of cost.
[other compositions]
In the scope not affecting effect of the present invention, also can mix other compositions beyond mentioned component as required in liquid washing agent of the present invention.
As other compositions, there is no particular limitation, can mix normally used composition in liquid detergent composition for clothes, concrete example composition shown below.
In order to improve appearance stability, in liquid washing agent of the present invention, also alkanolamine can be mixed.
Particularly, when mixed anion tensio-active agent is as tensio-active agent (A), alkanolamine is the composition that possible become anion surfactant gegenion, by mixed anion tensio-active agent, the white casse etc. being easy to produce can be suppressed, play the effect improving appearance stability.Therefore, in liquid washing agent of the present invention, above-mentioned tensio-active agent (A) while containing anion surfactant, also preferably further containing alkanolamine.
As alkanolamine, preferably as the alkanolamine that the gegenion of anion surfactant works; Preferably there is the alkanolamine of carbonatoms 1 ~ 3 alkyl; More preferably there is the alkanolamine of carbonatoms 1 ~ 2 alkyl; Preferred monoethanolamine, diethanolamine and trolamine further.
Alkanolamine can a kind ofly separately use, also can be two or more and use.
In liquid washing agent, the amount of alkanolamine is relative to liquid washing agent total mass preferably 0.1 ~ 3 quality %, more preferably 0.5 ~ 3 quality %, further preferred 0.5 ~ 2 quality %.
If the amount of alkanolamine relative to liquid washing agent total mass at more than 0.1 quality %, then the effect of this composition appearance stability that is easily improved.In addition, if the amount of alkanolamine relative to liquid washing agent total mass at below 3 quality %, be then easy to suppress because alkanolamine absorbs the generation of the recessed phenomenon of container that oxygen causes.
In order to improve cleaning force can and mixed stability etc., can mix in liquid washing agent of the present invention: the organic solvent beyond enzyme (proteolytic enzyme, lipase, cellulase etc.), (D) composition, thickening material (long-chain fat alkanol amides etc.), feel rising agent, pH adjusting agent, sanitas, fluorescent agent, move and contaminate preventing agent, pearling agent, antioxidant, stain remover etc.
From the viewpoint of liquid stability, as pH adjusting agent, preferably sulfuric acid, sodium hydroxide, potassium hydroxide etc.
Further, in order to improve the value added of commodity, liquid washing agent of the present invention can also mix fragrant agent, emulsifying agent etc.
As fragrant agent, flavor compositions A, B, C, D etc. of recording in table 11 ~ 18 of No. 2002-146399, Japanese Patent Laid-Open can be used.The amount of fragrant agent is relative to liquid washing agent total mass preferably 0.1 ~ 1 quality %.
As emulsifying agent, can for example there are: polystyrene emulsion, polyvinyl acetate emulsion etc., usually be suitable for the emulsion using solids component 30 ~ 50 quality %.As object lesson, for example there are: polystyrene emulsion (Saiden chemical company produces, " SaivinolRPX-196PE-3 ", solids component 40 quality %) etc.The amount of emulsifying agent is relative to liquid washing agent total mass preferably 0.01 ~ 0.5 quality %.
Liquid washing agent of the present invention is preferably 5 ~ 10 at the pH of 25 DEG C, and more preferably 5 ~ 9.5, further preferably 5 ~ 9, particularly preferably 6 ~ 9.
If the pH of liquid washing agent is more than lower value, when long-time preservation liquid washing agent, be easy to keep good cleaning force.If above-mentioned pH does not arrive higher limit, will more be easy to suppress the pigment dyeing to washing clothes.Also be easy to keep liquid stability well.
In this explanation, the pH value of liquid washing agent (temperature adjustment to 25 DEG C) represents the value measured according to pH meter (ProductName: HM-30G, DKK Toa Corp. manufactures) etc.
Liquid washing agent of the present invention is a kind of in the concentrated type liquid washing agent containing pigment, while having high cleaning force, inhibits the liquid washing agent to washing clothes pigment dyeing.
In the concentrated type liquid washing agent containing pigment, the following problem of easy generation: when the washing object (washing clothes) being coated with aforesaid liquid washing composition is temporarily placed or carries out once washing with roller washing machine etc. (, when rinsing is insufficient) etc., easily pigment dyeing is carried out to washing clothes.
This changes according to the impact of the kind of the composition of liquid washing agent, clothing (fiber), temperature and water temperature the easy generation of the pigment dyeing of washing clothes., more easily there is pigment dyeing in such as cold condition or the kind hydrophobic fibre (trevira etc.) according to organic solvent.
As the reason of washing clothes being carried out to pigment dyeing, be considered to: if the tensio-active agent of high density and washing clothes Long contact time, or because rinsing is insufficient and make surfactant moieties remain on washing clothes, tensio-active agent will too penetrate in clothing (fiber), pigment will be adsorbed onto the deep layer of clothes class (fiber) thereupon, and pigment easily dyes to washing clothes thus.
In addition, according to temperature condition and storage period, the moisture in liquid washing agent and solvent evaporation, composition gels, when can make washing, liquid washing agent can not fully dissolve in water.Therefore can think, because the tensio-active agent of high density and washing clothes are in the state of Long contact time, therefore pigment is easy to dye to washing clothes.
In liquid washing agent of the present invention, contain tensio-active agent, the pigment of more than 40 quality % relative to liquid washing agent total mass, simultaneously also containing urea or derivatives thereof (C).(C) composition is strongly hydrophilic material, is related to that itself and tensio-active agent have strong interaction on the other hand because of himself structural performance, therefore thinks that (C) composition is easily present in around surfactant molecule in the formulation.Thus during coating washing, due to the existence of (C) composition, tensio-active agent can be suppressed the absorption of clothing or infiltration, also can suppress the interaction of hydrophobic fibre and tensio-active agent.According to its result, supposition can obtain effect of the present invention.
According to liquid washing agent of the present invention, even if the washing clothes being coated with liquid washing agent is temporarily placed or rinsing is insufficient, the pigment dyeing to washing clothes also can be suppressed.
In addition, according to liquid washing agent of the present invention, by containing (C) composition, especially, also can suppress when and with suppressing the anion surfactant of secondary pollution and the liquid xanthochromia easily produced when can become the alkanolamine of above-mentioned anion surfactant gegenion, keep appearance stability well.
Liquid washing agent of the present invention, just can play high washing effect with a small amount of washing composition usage quantity.
Liquid washing agent of the present invention, is particularly suitable as dress material washing composition, is a kind of containing pigment while, also has the liquid washing agent of high surface agent concentration composition (concentrated composition).
As a kind of form of liquid washing agent of the present invention, be listed below liquid washing agent:
Liquid washing agent containing tensio-active agent (A), pigment (B), urea or derivatives thereof (C), organic solvent (D), relative to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40 ~ 70 quality %,
Above-mentioned (B) composition is 1 ~ 150ppm (quality criteria),
Above-mentioned (C) composition is 0.5 ~ 12 quality %,
Above-mentioned (D) composition is 5 ~ 20 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
As other forms of liquid washing agent of the present invention, be listed below liquid washing agent:
Liquid washing agent containing tensio-active agent (A), pigment (B), urea or derivatives thereof (C), water, relative to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40 ~ 70 quality %,
Above-mentioned (B) composition is 1 ~ 150ppm (quality criteria),
Above-mentioned (C) composition is 0.5 ~ 12 quality %,
Above-mentioned water is 15 ~ 45 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
As other forms of liquid washing agent of the present invention, be listed below liquid washing agent:
Liquid washing agent containing tensio-active agent (A), pigment (B), urea or derivatives thereof (C), organic solvent (D), water, relative to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40 ~ 70 quality %,
Above-mentioned (B) composition is 1 ~ 150ppm (quality criteria),
Above-mentioned (C) composition is 0.5 ~ 12 quality %,
Above-mentioned (D) composition is 5 ~ 20 quality %,
Above-mentioned water is 15 ~ 45 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
Embodiment
Further describe the present invention by embodiment below, but the present invention is not limited in these embodiments.In addition, " % " all represents " quality % " under the condition not having specified otherwise.
The composition of each routine liquid washing agent is as shown in table 1 ~ 3.
The raw material used in the present embodiment is as follows.
[tensio-active agent (A)]
A-1:C 11h 23cO-(OC 2h 4) 15-OCH 3, stenosis rate 33 quality %; Synthetics.A-1 produces according to the method recorded in Japanese Patent Laid-Open 2002-144179 publication.That is, be 2.5MgOAl by chemical constitution 2o 3nH 2aluminum magnesium hydroxide (the trade(brand)name: Kyoward300 of O, Kyowa Chemical Industry Co., Ltd produces) at 600 DEG C, in nitrogen environment, calcine calcinations of aluminum hydroxide Mg catalyst (unmodified) 2.2g obtained for 1 hour, potassium hydroxide-ethanol solution 2.9mL, the Laurate methyl 350g loading 4L autoclave specified as 0.5 of surface-modifying agent, in above-mentioned autoclave, carry out catalyst modification.Then, heat after carrying out nitrogen replacement in autoclave, while maintenance temperature 180 DEG C, pressure 3 × 105Pa, import 1079g oxyethane, make it react while stirring.
Subsequently, reaction solution is cooled to 80 DEG C, adds 159g water, as after the atlapulgite of filtration adjuvant and each 5g of diatomite, filtering catalyst obtains target compound A-1.
A-2:C 11h 23cO-(OC 2h 4) 15-OCH 3with C 13h 27cO-(OC 2h 4) 15-OCH 3mass ratio be the mixture of 8/2, stenosis rate 33 quality %; Synthetics.
But A-2 is in the synthesis of above-mentioned A-1, except Laurate methyl 350g being replaced with the mixture of Laurate methyl 280g and nutmeg acid 70g, import beyond oxyethane 1052g, with same synthetic method manufacture.
A-3: the nonionogenic tenside being the oxyethane of average 9 moles of block addition successively on the primary alconol of carbonatoms 10 ~ 14, the propylene oxide of average 2 moles, the oxyethane of average 9 moles.R in general formula (a3) 6the straight-chain alkyl of=carbonatoms 10 ~ 14, p=9, q=2, r=9.
A-4: the nonionogenic tenside being the oxyethane of average 9 moles of addition on the secondary alcohol of carbonatoms 12 ~ 14, trade(brand)name: SOFTANOL90, Nippon Shokubai Co., Ltd produces.R in general formula (a2) 4the branched-chain alkyl of=carbonatoms 12 ~ 14, t=9.
A-5: polyxyethylated (C12-13) ether.In raw alcohol SAFOL23 (trade(brand)name, the production of Sa Suoer company; The mass ratio of the alcohol of carbonatoms 12 and the alcohol of carbonatoms 13 is the mixture of C12/C13=55%/45%, is 50 quality % relative to the ratio of the linear carbon chain of all carbochains) product of upper average 15 moles of ethylene oxide of addition.
A-6: straight chained alkyl (carbonatoms 10 ~ 14) Phenylsulfonic acid [Lion Corporation produces, trade(brand)name: LIPONLH-200 (LAS-H purity 96 quality %)].
A-7:AES-Na, carbonatoms 12 ~ 13 Voranol EP 2001 sodium sulfate (the average addition mole number of oxyethane is 2), synthetics (raw alcohol trade(brand)name: Neodol23, Shell Co. Ltd produces).
A-8: be the product [LMAO (C12/14-15EO)] being equivalent to 12 moles of ethylene oxide in natural alcohol (P & G company produces, trade(brand)name: CO-1214) upper addition, synthetics.Synthesize as follows.
Get trade(brand)name " CO-1214 " 861.2g, 30 quality %NaOH aqueous solution 2.0g that P & G company produces, put into pressure resistant type reaction vessel, in container, use nitrogen replacement.Then, after 30 minutes, 160 DEG C are warming up in temperature 100 DEG C, below pressure 2.0kPa dehydration.Then limit stirring reaction liquid, while slowly add oxyethane (gas shape) 760.6g in reaction solution.Now, use and be blown into pipe, limit regulates interpolation speed to make temperature of reaction be no more than 180 DEG C of limits to add.After oxyethane interpolation terminates, in temperature 180 DEG C, below pressure 0.3MPa slaking after 30 minutes, in temperature 180 DEG C, below pressure 6.0kPa distillation 10 minutes, remove unreacted oxyethane.Then, temperature is cooled to after below 100 DEG C, adds 70 quality % tosic acid and neutralize, make the pH of the reactant 1 quality % aqueous solution be about 7, obtain LMAO (C12/14-15EO).
[pigment (B)]
B-1:C.I. Food Green 3, green No. 3, occasion change into Co., Ltd.'s production the sixth of the twelve Earthly Branches; Maximum absorption wavelength 610nm.
B-2:LiquitintBlueHP, Mei Liken Co., Ltd. produces; Maximum absorption wavelength 595nm, 645nm.
B-3:C.I. solvent blue 63, blue No. 403, occasion change into Co., Ltd.'s production the sixth of the twelve Earthly Branches; Maximum absorption wavelength 600nm, 645nm.
[pigment (C)]
C-1: urea, reagent, Junsei Chemical Co., Ltd. produces.
C-2:1,3-dimethyl urea, reagent, Tokyo HuaCheng Industry Co., Ltd produces.
[organic solvent (D) that general formula (d1) represents]
D-1:1,2-propylene glycol (trade(brand)name Propyleneglycol, Showa Denko K. K produces) purity 100 quality %.R in general formula (d1) 7=hydroxyl, m=1, n=0.
D-2: butyl (trade(brand)name Butyldiglycol, Japanese emulsifying agent Co., Ltd. produces) purity 100 quality %.R in general formula (d1) 7=ethyl, m=0, n=3.
D-3: ethanol (the specific alcohol of trade(brand)name 95 degree of synthetic alcohols, Japanese alcohol is sold Co., Ltd. and produced).R in general formula (d1) 7=hydrogen atom, m=0, n=1.
[other compositions]
MEA: monoethanolamine (Nippon Shokubai Co., Ltd's production) purity 100 quality %.
DEA: diethanolamine (Nippon Shokubai Co., Ltd's production) purity 100 quality %.
Polyoxyethylene glycol: Shi Wang KCC produces, trade(brand)name " PEG#1000-L60 ", the polymerization degree 20.
Enzyme: proteolytic enzyme, trade(brand)name " Everlase16LTypeEX ", Novozymes Company produces.
Citric acid: Fukawa Chemical Industries Co., Ltd. produces, purity 100 quality %.
PH adjusting agent: KOH (Asahi Glass Co., Ltd's production) and sulfuric acid (Toho Zinc Co., Ltd.'s production).
Ion exchanged water.
The Production Example > of < liquid washing agent
According to mixing element, the amount (quality %) of composition table 1 ~ 3 Suo Shi, the liquid washing agent manufacturing each example according to following manufacture method respectively (in table, is space if any mixing element, does not then mix this mixing element.)
In table, the amount of mixing element represents with purity conversion amount.In addition, the amount of (B) composition is only had to represent with " ppm " (quality criteria).
Represent that " balance " of water amount represents that the total amount of the liquid washing agent of the final preparation of adjustment is to combined amount during 100 quality %.
Represent combined amount when " in right amount " of pH adjusting agent amount represents rearrange liquids washing composition pH (25 DEG C) pH that arrives that it is as shown in the table.
" mass ratio: (A)/(C) " represents the amount relative to (C) composition in liquid washing agent, the ratio (mass ratio) of (A) composition amount.
(embodiment 1 ~ 19, comparative example 1 ~ 3, reference example 1)
Respectively according to the amount (quality %) shown in table, (D) composition, polyoxyethylene glycol, MEA or DEA, A-6 or A-7 are added in 500mL beaker and carries out stirring (in addition, be space if any mixing element in table, then do not mix this mixing element).Then, (C) component solution (concentration 50 quality %) of (C) composition and citric acid being dissolved in separately and being formed in water is added and aqueous citric acid solution (concentration 50 quality %) stirs.
Then, by pH adjusting agent, the pH (25 DEG C) of solution is adjusted to the value shown in table.
Then, add remaining (A) composition to stir.Add enzyme afterwards to stir, then add the pigment aqueous solution (pigment concentration 1000ppm) that formed in water by (B) component dissolves and determine concentration to institute, stirring.Thereafter, add ion exchanged water and make the total amount of final preparation to 100 quality %, obtain the liquid washing agent of each example thus respectively.
The pH (25 DEG C) of solution measures as follows: use pH meter (ProductName: HM-30G, DKK Toa Corp. produce), in the solution of temperature adjustment to 25 DEG C, puts into the electrode of above-mentioned pH meter, reads the value measured after 2 minutes.
The evaluation > of < liquid washing agent
According to evaluation method shown below, the liquid washing agent of each example is carried out respectively to the evaluation of " coating cleaning force ", " pigment dyeing to clothing " and " appearance stability ".It the results are shown in table 1 ~ 3.
[coating cleaning force]
Pollute the preparation of cloth
By oiliness marker pen (marker pen ink/superfine M700-T1) inking back and forth equably on cotton fabrics (5cm × 5cm), blacking becomes round shape (diameter 2cm), every example makes 5 pieces, as the pollution cloth of coating cleaning force evaluation.
(wash conditions)
With relative to water 30L standard usage quantity (concentrated type 10g/ water 30L, usual type 20g/ water 30mL) liquid washing agent to above-mentioned 5 pieces pollute cloth every 1 piece be coated with after, at temperature 20 DEG C place 5 minutes.Specifically, every 1 piece of glue spread polluting the liquid washing agent of cloth is respectively 0.3g in embodiment 1 ~ 19, comparative example 1 ~ 3 (concentrated type), is 0.6g in reference example 1.
Thereafter, in Terg-o-tometer (production of UnitedStatesTesting company), 3 ° of DH hard water 900ml, above-mentioned pollution cloth 5 pieces and cotton underwear (the LL size of 15 DEG C is doubly put into bath raio 20, DVD commercial firm produces) fritter (about 3cm × 3cm) that is cut into, washing 10 minutes under 120rpm, the condition of 15 DEG C.
(rinsing condition)
After above-mentioned washing, dewater 1 minute, subsequently, in 3 ° of DH hard water 900ml of 15 DEG C, rinsing 3 minutes under 120rpm, the condition of 15 DEG C.This dehydration and rinsing carry out 2 times repeatedly.
(drying conditions)
After 2nd rinsing, dewater 1 minute, subsequently, the every block pollution cloth after washing is all clipped in filter paper and carries out drying with electric iron.
The evaluation of coating cleaning force is by before washing and after washing, with albedometer (beam splitting type colour-difference meter SE2000, electricity Se Industrial Co., Ltd of Japan manufactures) measure reflectivity (Z value), calculate cleaning rate (%) to carry out according to following formula.
Cleaning rate (%)=(the Z value of the pollution cloth before the Z value-washing of the pollution cloth after washing)/(the Z value of the pollution cloth before the Z value-washing of former cloth) × 100
In formula, " former cloth " refers to the cotton knitwear not implementing pollution plot in the preparation of above-mentioned pollution cloth.
Calculate the cleaning rate (%) of 5 pieces of pollution cloth of each example respectively, obtain its mean value, according to following metewand evaluation coating cleaning force.◎, zero, △ is qualified.
Metewand
◎: the mean value of cleaning rate (%) is more than 15%.
Zero: the mean value of cleaning rate (%) more than 10%, less than 15%.
△: the mean value of cleaning rate (%) more than 5%, less than 10%.
×: the mean value of cleaning rate (%) is less than 5%.
[evaluation to the pigment dyeing of clothing]
The end (thickening place, sewn portion) of only white being wiped hand cotton towel (29cm × 72cm) long side direction is cut, as evaluation with trial target (cotton) (quality 5g part)
Subsequently, the liquid washing agent of 5g in the liquid washing agent standard usage quantity (15g) of relative washes 4kg is coated on evaluation trial target (cotton), places 12 hours.
Thereafter, using being coated with the above-mentioned evaluation trial target (cotton) of 5g lotion and putting into washing machine as the common 4kg of the cotton underwear loading cloth, add remaining liquid washing agent and wash.
Wash conditions now sets as follows.Washing machine uses Toshiba's drum-type washing machine (ProductName: TW-4000VFL).Washing procedure is: washing time 10 minutes, and rinsing specifies 1 time, dewaters 8 minutes.
More than operate (during cotton towel) supposing to carry out under summer and the condition in supposition winter respectively.
Assuming that during summer, the evaluation trial target (cotton) that will be coated with 5g liquid washing agent is placed 12 hours temperature 25 DEG C, uses temperature adjustment to the water of 25 DEG C during washing.
Assuming that during winter, the evaluation trial target (cotton) that will be coated with 5g liquid washing agent is placed 12 hours temperature 5 DEG C, uses temperature adjustment to the water of 5 DEG C during washing.
In addition, polyester (PE) sweat shirt (valley head shop) is cut 5cm × 5cm, as evaluation with trial target (PE) (quality 0.2g part).
Subsequently, the liquid washing agent of 2g in the liquid washing agent standard usage quantity (15g) of relative washes 4kg is coated on evaluation trial target (PE), places 12 hours.
Thereafter, using being coated with the above-mentioned evaluation trial target (PE) of 5g lotion and putting into washing machine as the common 4kg of the cotton underwear loading cloth, add remaining liquid washing agent, wash with the condition identical with above-mentioned wash conditions.
More than operate (during PE) only with the similarity condition in above-mentioned supposition summer under carry out.
Then, whether visual judgement evaluation trial target (cotton) after washing, evaluation trial target (PE) can confirm pigment dyeing, evaluate according to following metewand.◎, zero, △ is qualified.
Metewand
◎: the evaluation trial target after washing confirms completely less than pigment dyeing.
Zero: the evaluation trial target after washing only confirms considerably less pigment dyeing.
△: the evaluation trial target after washing confirms a small amount of pigment dyeing.
×: the evaluation trial target after washing confirms obvious pigment dyeing.
[appearance stability]
Immediately the liquid washing agent 100g of each example is put into cylindrical glass bottle (PS100) after manufacture, close lid sealing, preserve 30 at 50 DEG C.
Then, visual outward appearance (liquid color) change judging the liquid washing agent after preserving, evaluates according to following metewand.◎, zero is qualified.
In addition, when causing liquid washing agent xanthochromia because preserving, before keeping, (initial stage) was blue become green originally, and the initial stage was green become yellow-green colour originally.
Metewand
◎: compare with preliminary phase, confirms to change less than outward appearance (liquid color) completely.
Zero: slightly confirm following change respectively: the initial stage was blue become green originally, the initial stage was green become yellow-green colour originally.
×: obviously confirm following change respectively: the initial stage was blue become green originally, the initial stage was green become yellow-green colour originally.
Table 2
Table 3
Can be confirmed by the result of table 1 ~ 3, the liquid washing agent of embodiment 1 ~ 19, while having high cleaning force, further suppress the pigment dyeing to washing clothes.
Industrial utilizes possibility
The present invention, in the concentrated type liquid washing agent containing pigment, can provide a kind of while having high cleaning force, further suppress the liquid washing agent of the pigment dyeing to washing clothes, thus industrially very useful.

Claims (9)

1. a liquid washing agent, contains: the urea of the tensio-active agent (A) of more than 40 quality %, the pigment (B) of below quality criteria 150ppm, 0.5 ~ 12 quality % or 1,3-dimethyl urea (C),
Described tensio-active agent (A) containing at least one tensio-active agent be selected from nonionogenic tenside that following general formula (a1) ~ (a3) represent,
R 1CO-(OR 2) s-OR 3…(a1)
R 4-O-(R 5O) t-H…(a2)
R 6-O-[(EO) p/(PO) q]-(EO) r-H…(a3)
In formula (a1), R 1for the straight-chain of carbonatoms 5 ~ 21 or the alkyl of branched or thiazolinyl, R 2for the alkylidene group of carbonatoms 2 ~ 4, R 3for the alkyl of carbonatoms 1 ~ 4, s represents OR 2average repeat unit number, be the numeral of 5 ~ 30; In formula (a2), R 4for the alkyl of carbonatoms 10 ~ 22, R 5for the alkylidene group of carbonatoms 2 ~ 4, t represents R 5the average repeat unit number of O is the numeral of 5 ~ 20; In formula (a3), R 6for alkyl or the thiazolinyl of carbonatoms 10 ~ 16, p represents the average repeat unit number of EO, q represents the average repeat unit number of PO, r represents the average repeat unit number of EO, p, q, r are for meeting the integer of p > 1, r≤0,0 < q≤3 and p+r=10 ~ 30, and EO represents oxyethylene group, and PO represents oxypropylene group, (EO) EO and PO in p/ (PO) q also can mix arrangement
(A) in composition, relative to (A) composition nonionogenic tenside at more than 50 quality %.
2. liquid washing agent according to claim 1, further containing anion surfactant in (A) composition.
3. liquid washing agent according to claim 2, the amount of anion surfactant is 1 ~ 10 quality % relative to liquid washing agent total mass.
4. liquid washing agent according to claim 1 and 2, it is further containing the organic solvent (D) that following general formula (d1) represents,
R 7-[(EO) n/(PO) m]-H…(d1)
In formula, R 7for the alkyl of hydrogen atom, hydroxyl or carbonatoms 1 ~ 4; M represents the average repeat unit number of PO, and n represents the average repeat unit number of EO, and m is the integer of 0 ~ 2, and n is the integer of 0 ~ 3, and 1≤m+n≤5, and EO represents oxyethylene group, and PO represents oxypropylene group, EO and PO also can mix arrangement.
5. liquid washing agent as claimed in claim 1 or 2, the mass ratio that (A)/(C) represents is below 30.
6. liquid washing agent as claimed in claim 2, in tensio-active agent (A), nonionogenic tenside is selected from least a kind in formula (a1), (a2),
Anion surfactant is selected from least a kind in alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate salt.
7. liquid washing agent as claimed in claim 1 or 2, pigment (B) is the pigment having maximum absorption wavelength at 400 ~ 700nm.
8. liquid washing agent as claimed in claim 1 or 2, pigment (B) is for being selected from C.I. acid blue 5, C.I. acid blue 9, C.I. Acid Blue 74, C.I. solvent blue 19 1, C.I. solvent blue 19 2, C.I. solvent blue 36, C.I. solvent blue 63, C.I. EX-SF DISPERSE BLUE EX-SF 300 1, C.I. EX-SF DISPERSE BLUE EX-SF 300 3, C.I. EX-SF DISPERSE BLUE EX-SF 300 5, C.I. EX-SF DISPERSE BLUE EX-SF 300 6, C.I. EX-SF DISPERSE BLUE EX-SF 300 7, C.I. EX-SF DISPERSE BLUE EX-SF 300 26, C.I. EX-SF DISPERSE BLUE EX-SF 300 27, C.I. EX-SF DISPERSE BLUE EX-SF 300 54, C.I. EX-SF DISPERSE BLUE EX-SF 300 55, C.I. Disperse Blue-56, C.I. Disperse Blue-60, C.I. EX-SF DISPERSE BLUE EX-SF 300 61, C.I. EX-SF DISPERSE BLUE EX-SF 300 62, C.I. EX-SF DISPERSE BLUE EX-SF 300 64, C.I. EX-SF DISPERSE BLUE EX-SF 300 72, C.I. EX-SF DISPERSE BLUE EX-SF 300 73, C.I. EX-SF DISPERSE BLUE EX-SF 300 81, C.I. EX-SF DISPERSE BLUE EX-SF 300 87, C.I. EX-SF DISPERSE BLUE EX-SF 300 90, C.I. EX-SF DISPERSE BLUE EX-SF 300 91, C.I. EX-SF DISPERSE BLUE EX-SF 300 97, C.I. EX-SF DISPERSE BLUE EX-SF 300 98, C.I. EX-SF DISPERSE BLUE EX-SF 300 99, C.I. EX-SF DISPERSE BLUE EX-SF 300 103, C.I. EX-SF DISPERSE BLUE EX-SF 300 104, C.I. EX-SF DISPERSE BLUE EX-SF 300 105, C.I. Blue 7, C.I. vat blue 1, C.I. reductive blue 6, one kind or two or more in the pigment of C.I. pigment indigo plant 15.
9. liquid washing agent as claimed in claim 4, (D) composition is 5 ~ 20% relative to the total mass of liquid washing agent.
CN201280016756.4A 2011-04-01 2012-03-28 Liquid washing agent Expired - Fee Related CN103459579B (en)

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